POLYMER CHEMISTRY

INTRODUCTION

Radical Additions to Alkenes: Polymers

Radicals can add to alkene double bonds, taking one electron from the double bond and leaving
one behind to yield a new radical. Let’s now look at the process in more detail, focusing on the industrial
synthesis of alkene polymers.

A polymer is simply a large—sometimes very large—molecule built up by repetitive bonding

together of many smaller molecules, called monomers. Nature makes wide use of biological polymers.
Cellulose, for instance, is a polymer built of repeating glucose monomer units; proteins are polymers built
of repeating amino acid monomers; and nucleic acids are polymers built of repeating nucleotide
monomers. Synthetic polymers, such as polyethylene, are chemically much simpler than biopolymers, but
there is still a great diversity to their structures and properties, depending on the identity of the
monomers and on the reaction conditions used for polymerization.
 The simplest synthetic polymers are those that result when an alkene is treated with a small
amount of a radical as catalyst. Ethylene, for example, yields polyethylene, an enormous alkane that may
have up to 200,000 monomer units incorporated into a gigantic hydrocarbon chain. Approximately 14
million tons per year of polyethylene is manufactured in the United States alone.

Historically, ethylene polymerization was carried out at high pressure (1000–3000 atm) and high
temperature (100–250 °C) in the presence of a catalyst such as benzoyl peroxide, although other catalysts
and reaction conditions are now more often used. The key step is the addition of a radical to the ethylene
double bond, a reaction similar in many respects to what takes place in the addition of an electrophile. In
writing the mechanism, recall that a curved halfarrow, or “fishhook”, is used to show the movement of a
single electron, as opposed to the full curved arrow used to show the movement of an electron pair in a
polar reaction.

 Initiation The polymerization reaction is initiated when a few radicals are generated on heating a
small amount of benzoyl peroxide catalyst to break the weak O-O bond. A benzoyloxy radical then
adds to the C=C bond of ethylene to generate a carbon radical. One electron from the C=C bond
pairs up with the odd electron on the benzoyloxy radical to form a C-O bond, and the other
electron remains on carbon.

 Propagation Polymerization occurs when the carbon radical formed in the initiation step adds to
another ethylene molecule to yield another radical. Repetition of the process for hundreds or
thousands of times builds the polymer chain.
  Termination The chain process is eventually ended by a reaction that consumes the radical.
Combination of two growing chains is one possible chain terminating reaction.

Ethylene is not unique in its ability to form a polymer. Many substituted ethylenes, called vinyl
monomers, also undergo polymerization to yield polymers with substituent groups regularly spaced on
alternating carbon atoms along the chain. Propylene, for example, yields polypropylene, and styrene
yields polystyrene.

When an unsymmetrically substituted vinyl monomer such as propylene or styrene is polymerized,

the radical addition steps can take place at either end of the double bond to yield either a primary radical
intermediate (RCH2·) or a secondary radical (R2CH·). Just as in electrophilic addition reactions, however,
we find that only the more highly substituted, secondary radical is formed.

Table 7.1 shows some commercially important alkene polymers, their uses, and the vinyl monomers
from which they are made.
Polyamides and Polyesters: Step-Growth Polymers
When an amine reacts with an acid chloride, an amide is formed. What would happen, though, if
a diamine and a diacid chloride were allowed to react? Each partner could form two amide bonds, linking
more and more molecules together until a giant polyamide resulted. In the same way, reaction of a diol
with a diacid would lead to a polyester.

The alkene and diene polymers discussed in Sections 7.10 and 14.6 are called chain-growth
polymers because they are produced by chain reactions. An initiator adds to a C=C bond to give a reactive
intermediate, which adds to a second alkene molecule to produce a new intermediate, which adds to a
third molecule, and so on. By contrast, polyamides and polyesters are called step-growth polymers
because each bond in the polymer is formed independently of the others. A large number of different
step-growth polymers have been made; some of the more important ones are shown in Table 21.2
Polyamides (Nylons)
The best known step-growth polymers are the polyamides, or nylons, first prepared by Wallace
Carothers at the DuPont Company by heating a diamine with a diacid. For example, nylon 66 is prepared
by reaction of adipic acid (hexanedioic acid) with hexamethylenediamine (1,6 - hexanediamine) at 280°C.
The designation “66” tells the number of carbon atoms in the diamine (the first 6) and the diacid (the
second 6).

Nylons are used both in engineering applications and in making fibers. A combination of high
impact strength and abrasion resistance makes nylon an excellent metal substitute for bearings and gears.
As fiber, nylon is used in a variety of applications, from clothing to tire cord to ropes.

Polyesters
The most generally useful polyester is that made by reaction between dimethyl terephthalate
(dimethyl 1,4-benzenedicarboxylate) and ethylene glycol (1,2-ethanediol). The product is used under the
trade name Dacron to make clothing fiber and tire cord and under the name Mylar to make recording
tape. The tensile strength of poly(ethylene terephthalate) film is nearly equal to that of steel.

Lexan, a polycarbonate prepared from diphenyl carbonate and bisphenol A, is another

commercially valuable polyester. Lexan has an unusually high impact strength, making it valuable for use
in telephones, bicycle safety helmets, and laptop computer cases.
Sutures and Biodegradable Polymers
Because plastics are too often thrown away rather than recycled, much work has been carried out
on developing biodegradable polymers, which can be broken down rapidly in landfills by soil
microorganisms. Among the most common biodegradable polymers are poly(glycolic acid) (PGA),
poly(lactic acid) (PLA), and polyhydroxybutyrate (PHB). All are polyesters and are therefore susceptible to
hydrolysis of their ester links. Copolymers of PGA with PLA have found a particularly wide range of uses.
A 90/10 copolymer of poly(glycolic acid) with poly(lactic acid) is used to make absorbable sutures, for
instance. The sutures are entirely hydrolyzed and absorbed by the body within 90 days after surgery.

In Europe, interest has centered particularly on polyhydroxybutyrate, which can be made into
films for packaging as well as into molded items. The polymer degrades within 4 weeks in landfills, both
by ester hydrolysis and by an E1cB elimination reaction of the oxygen atom β to the carbonyl group. The
use of polyhydroxybutyrate is limited at present by its cost—about four times that of polypropylene.
 Synthetic Polymers
Polymers are a fundamental part of the modern world, showing up in everything from coffee cups
to cars to clothing. In medicine, too, their importance is growing for purposes as diverse as cardiac
pacemakers, artificial heart valves, and biodegradable sutures.
We’ve seen on several occasions in previous chapters that a polymer, whether synthetic or
biological, is a large molecule built up by repetitive bonding together of many smaller units, or monomers.
Polyethylene, for instance, is a synthetic polymer made from ethylene (Section 7.10), nylon is a synthetic
polyamide made from a diacid and a diamine (Section 21.9), and proteins are biological polyamides made
from amino acids. Note that polymers are often drawn by indicating their repeating unit in parentheses.
The repeat unit in polystyrene, for example, comes from the monomer styrene.

Our treatment of polymers has thus far been dispersed over several chapters, but it’s now time
to take a more comprehensive view. In the present chapter, we’ll look further at how polymers are made,
and we’ll see how polymer structure correlates with physical properties. No course in organic chemistry
would be complete without a look at polymers.

Chain-Growth Polymers
Synthetic polymers are classified by their method of synthesis as either chain-growth or step-
growth. The categories are somewhat imprecise but nevertheless provide a useful distinction. Chain-
growth polymers are produced by chain-reaction polymerization in which an initiator adds to a carbon–
carbon double bond of an unsaturated substrate (a vinyl monomer) to yield a reactive intermediate. This
intermediate reacts with a second molecule of monomer to yield a new intermediate, which reacts with
a third monomer unit, and so on.
The initiator can be a radical, an acid, or a base. Historically, as we saw in Section 7.10, radical
polymerization was the most common method because it can be carried out with practically any vinyl
monomer. Acid-catalyzed (cationic) polymerization, by contrast, is effective only with vinyl monomers
that contain an electron-donating group (EDG) capable of stabilizing the chain-carrying carbocation
intermediate. Thus, isobutylene (2-methylpropene) polymerizes rapidly under cationic conditions, but
ethylene, vinyl chloride, and acrylonitrile do not. Isobutylene polymerization is carried out commercially
at -80 °C, using BF3 and a small amount of water to generate BF3OH⁻ H⁺ catalyst. The product is used in
the manufacture of truck and bicycle inner tubes.
 Vinyl monomers with electron-withdrawing substituents (EWG) can be polymerized by basic
(anionic) catalysts. The chain-carrying step is conjugate nucleophilic addition of an anion to the
unsaturated monomer (Section 19.13).

Acrylonitrile (H2C=CHCN), methyl methacrylate [H2C=C(CH3)CO2CH3], and styrene (H2C=CHC6H5)

can all be polymerized anionically. The polystyrene used in foam coffee cups, for example, is prepared by
anionic polymerization of styrene using butyllithium as catalyst.

An interesting example of anionic polymerization accounts for the remarkable properties of

“super glue,” one drop of which can support up to 2000 lb. Super glue is simply a solution of pure methyl
α-cyanoacrylate, which has two electron-withdrawing groups that make anionic addition particularly easy.
Trace amounts of water or bases on the surface of an object are sufficient to initiate polymerization of
the cyanoacrylate and bind articles together. Skin is a good source of the necessary basic initiators, and
many people have found their fingers stuck together after inadvertently touching super glue. So good is
super glue at binding tissues together that related cyanoacrylate esters such as Dermabond are used in
hospitals in place of sutures to close wounds.
 Stereochemistry of Polymerization:
Ziegler–Natta Catalysts
Although we didn’t point it out previously, the polymerization of a substituted vinyl monomer can
lead to a polymer with numerous chirality centers in its chain. For example, propylene might polymerize
with any of the three stereochemical outcomes shown in Figure 31.1. The polymer having all methyl
groups on the same side of the zigzag backbone is called isotactic, the one in which the methyl groups
alternate regularly on opposite sides of the backbone is called syndiotactic, and the one having the methyl
groups randomly oriented is called atactic.

The three different stereochemical forms of polypropylene all have somewhat different
properties, and all can be made by using the right polymerization catalyst. Propylene polymerization using
radical initiators does not work well, but polymerization using Ziegler–Natta catalysts allows preparation
of isotactic, syndiotactic, and atactic polypropylene.
Ziegler–Natta catalysts—there are many different formulations—are organometallic transition-
metal complexes prepared by treatment of an alkyl-aluminum with a titanium compound.
Triethylaluminum and titanium tetrachloride form a typical preparation.

Following their introduction in 1953, Ziegler–Natta catalysts revolutionized the field of polymer
chemistry because of two advantages: the resultant polymers are linear, with practically no chain
branching, and they are stereochemically controllable. Isotactic, syndiotactic, and atactic forms can all be
produced, depending on the catalyst system used.
The active form of a Ziegler–Natta catalyst is an alkyltitanium intermediate with a vacant coordination site
on the metal. Coordination of alkene monomer to the titanium occurs, and the coordinated alkene then
inserts into the carbon–titanium bond to extend the alkyl chain. A new coordination site opens up during
the insertion step, so the process repeats indefinitely.
 The linear polyethylene produced by the Ziegler–Natta process, called high-density polyethylene,
is a highly crystalline polymer with 4000 to 7000 ethylene units per chain and molecular weights in the
range 100,000 to 200,000 amu. High-density polyethylene has greater strength and heat resistance than
the branched product of radical-induced polymerization, called low-density polyethylene, and is used to
produce plastic squeeze bottles and molded housewares.
Polyethylenes of even higher molecular weights are produced for specialty applications. So-called
high-molecular-weight (HMW) polyethylene contains 10,000 to 18,000 monomer units per chain (MW =
300,000–500,000 amu) and is used for pipes and large containers. Ultrahigh-molecular-weight (UHMW)
polyethylene contains more than 100,000 monomer units per chain and has molecular weights ranging
from 3,000,000 to 6,000,000 amu. It is used in bearings, conveyor belts, and bulletproof vests among
other applications requiring unusual wear resistance.

Copolymers
Up to this point we’ve discussed only homopolymers—polymers that are made up of identical
repeating units. In practice, however, copolymers are more important commercially. Copolymers are
obtained when two or more different monomers are allowed to polymerize together. For example,
copolymerization of vinyl chloride with vinylidene chloride (1,1-dichloroethylene) in a 1:4 ratio leads to
the polymer Saran.

Copolymerization of monomer mixtures often leads to materials with properties quite different
from those of either corresponding homopolymer, giving the polymer chemist a vast amount of flexibility
for devising new materials. Table 31.1 lists some common copolymers and their commercial applications.
 Several different types of copolymers can be defined, depending on the distribution of monomer
units in the chain. If monomer A is copolymerized with monomer B, for instance, the resultant product
might have a random distribution of the two units throughout the chain, or it might have an alternating
distribution.

The exact distribution of monomer units depends on the initial proportions of the two reactant
monomers and their relative reactivities. In practice, neither perfectly random nor perfectly alternating
copolymers are usually found. Most copolymers have many random imperfections.
Two other forms of copolymers that can be prepared under certain conditions are called block
copolymers and graft copolymers. Block copolymers are those in which different blocks of identical
monomer units alternate with each other; graft copolymers are those in which homopolymer branches
of one monomer unit are “grafted” onto a homopolymer chain of another monomer unit.

Block copolymers are prepared by initiating the polymerization of one monomer as if growing a
homopolymer chain and then adding an excess of the second monomer to the still-active reaction mix.
Graft copolymers are made by gamma irradiation of a completed homopolymer chain in the presence of
the second monomer. The high-energy irradiation knocks hydrogen atoms off the homopolymer chain at
random points, thus generating radical sites that can initiate polymerization of the added monomer.

Step-Growth Polymers
Step-growth polymers are produced by reactions in which each bond in the polymer is formed
stepwise, independently of the others. Like the polyamides (nylons) and polyesters that we saw in Section
21.9, most step-growth polymers are produced by reaction between two difunctional reactants. Nylon 66,
for instance, is made by reaction between the six-carbon adipic acid and the six-carbon
hexamethylenediamine (1,6-hexanediamine). Alternatively, a single reactant with two different functional
groups can polymerize. Nylon 6 is made by polymerization of the six-carbon caprolactam. The reaction is
initiated by addition of a small amount of water, which hydrolyzes some caprolactam to 6-aminohexanoic
acid. Nucleophilic addition of the amino group to caprolactam then propagates the polymerization.

Polycarbonates
Polycarbonates are like polyesters, but their carbonyl group is linked to two -OR groups,
[O=C(OR)2]. Lexan, for instance, is a polycarbonate prepared from diphenyl carbonate and a diphenol
called bisphenol A. Lexan has an unusually high impact strength, making it valuable for use in machinery
housings, telephones, bicycle safety helmets, and bulletproof glass.
Polyurethanes
A urethane is a carbonyl-containing functional group in which the carbonyl carbon is bonded to
both an -OR group and an -NR2 group. As such, a urethane is halfway between a carbonate and a urea.

A urethane is typically prepared by nucleophilic addition reaction between an alcohol and an

isocyanate (R-N=C=O), so a polyurethane is prepared by reaction between a diol and a diisocyanate. The
diol is usually a low-molecular-weight polymer (MW ≈ 1000 amu) with hydroxyl end-groups; the
diisocyanate is often toluene-2,4-diisocyanate.

Several different kinds of polyurethanes are produced, depending on the nature of the polymeric
alcohol used. One major use of polyurethane is in the stretchable spandex fibers used for bathing suits
and athletic gear. These polyurethanes have a fairly low degree of cross-linking, so the resultant polymer
is soft and elastic. A second major use of polyurethanes is in the foams used for insulation. Foaming occurs
when a small amount of water is added during polymerization, giving a carbamic acid intermediate that
spontaneously loses bubbles of CO2.

Polyurethane foams are generally made using a polyalcohol rather than a diol as the monomer,
so the polymer has a high amount of three-dimensional cross-linking. The result is a rigid but very light
foam suitable for use as thermal insulation in building construction and portable ice chests.

Polymer Structure and Physical Properties

Polymers aren’t really that different from other organic molecules. They’re much larger, of course,
but their chemistry is similar to that of analogous small molecules. Thus, the alkane chains of polyethylene
undergo radical-initiated halogenation, the aromatic rings of polystyrene undergo typical electrophilic
aromatic substitution reactions, and the amide linkages of a nylon are hydrolyzed by aqueous base.
 The major difference between small and large organic molecules is in their physical properties.
For instance, their large size means that polymers experience substantially larger van der Waals forces
than do small molecules (Section 2.13). But because van der Waals forces operate only at close distances,
they are strongest in polymers like high-density polyethylene, in which chains can pack together closely
in a regular way. Many polymers, in fact, have regions that are essentially crystalline. These regions, called
crystallites, consist of highly ordered portions in which the zigzag polymer chains are held together by van
der Waals forces (Figure 31.2).

As you might expect, polymer crystallinity is strongly affected by the steric requirements of
substituent groups on the chains. Linear polyethylene is highly crystalline, but poly(methyl methacrylate)
is noncrystalline because the chains can’t pack closely together in a regular way. Polymers with a high
degree of crystallinity are generally hard and durable. When heated, the crystalline regions melt at the
melt transition temperature, Tm, to give an amorphous material.
Noncrystalline, amorphous polymers like poly(methyl methacrylate), sold under the trade name
Plexiglas, have little or no long-range ordering among chains but can nevertheless be very hard at room
temperature. When heated, the hard amorphous polymer becomes soft and flexible at a point called the
glass transition temperature, Tg. Much of the art in polymer synthesis lies in finding methods for
controlling the degree of crystallinity and the glass transition temperature, thereby imparting useful
properties to the polymer.
In general, polymers can be divided into four major categories, depending on their physical
behavior: thermoplastics, fibers, elastomers, and thermosetting resins. Thermoplastics are the polymers
most people think of when the word plastic is mentioned. These polymers have a high Tg and are therefore
hard at room temperature but become soft and viscous when heated. As a result, they can be molded
into toys, beads, telephone housings, or any of a thousand other items. Because thermoplastics have little
or no cross-linking, the individual chains can slip past one another in the melt. Some thermoplastic
polymers, such as poly(methyl methacrylate) and polystyrene, are amorphous and noncrystalline; others,
such as polyethylene and nylon, are partially crystalline. Among the better-known thermoplastics is
poly(ethylene terephthalate), or PET, used for making plastic soft-drink bottles.
 Plasticizers—small organic molecules that act as lubricants between chains—are usually added
to thermoplastics to keep them from becoming brittle at room temperature. An example is poly(vinyl
chloride), which is brittle when pure but becomes supple and pliable when a plasticizer is added. In fact,
most drip bags used in hospitals to deliver intravenous saline solutions are made of poly(vinyl chloride),
although replacements are appearing. Dialkyl phthalates such as di(2-ethylhexyl) phthalate (generally
called dioctyl phthalate) are commonly used as plasticizers, although questions about their safety have
been raised. The U.S. Food and Drug Administration (FDA) has advised the use of alternative materials in
compromised patients and infants but has found no evidence of toxicity for most patients.

Fibers are thin threads produced by extruding a molten polymer through small holes in a die, or
spinneret. The fibers are then cooled and drawn out, which orients the crystallite regions along the axis
of the fiber and adds considerable tensile strength (Figure 31.3). Nylon, Dacron, and polyethylene all have
the semicrystalline structure necessary for drawing into oriented fibers.
Elastomers are amorphous polymers that have the ability to stretch out and spring back to their
original shapes. These polymers must have low Tg values and a small amount of cross-linking to prevent
the chains from slipping over one another. In addition, the chains must have an irregular shape to prevent
crystallite formation. When stretched, the randomly coiled chains straighten out and orient along the
direction of the pull. Van der Waals forces are too weak and too few to maintain this orientation, however,
and the elastomer therefore reverts to its random coiled state when the stretching force is released
(Figure 31.4).
 Natural rubber (Chapter 7 Focus On) is the most common example of an elastomer. Rubber has
the long chains and occasional cross-links needed for elasticity, but its irregular geometry prevents close
packing of the chains into crystallites. Gutta-percha, by contrast, is highly crystalline and is not an
elastomer (Figure 31.5).

Thermosetting resins are polymers that become highly cross-linked and solidify into a hard,
insoluble mass when heated. Bakelite, a thermosetting resin first produced in 1907, has been in
commercial use longer than any other synthetic polymer. It is widely used for molded parts, adhesives,
coatings, and even high-temperature applications such as missile nose cones.
Chemically, Bakelite is a phenolic resin, produced by reaction of phenol and formaldehyde. On
heating, water is eliminated, many cross-links form, and the polymer sets into a rocklike mass. The cross-
linking in Bakelite and other thermosetting resins is three-dimensional and is so extensive that we can’t
really speak of polymer “chains.” A piece of Bakelite is essentially one large molecule.
SUMMARY AND KEY WORDS
Synthetic polymers can be classified as either chain-growth polymers or step-growth polymers.
Chain-growth polymers are prepared by chain-reaction polymerization of vinyl monomers in the presence
of a radical, an anion, or a cation initiator. Radical polymerization is sometimes used, but alkenes such as
2-methylpropene that have electron-donating substituents on the double bond polymerize easily by a
cationic route through carbocation intermediates. Similarly, monomers such as methyl α-cyanoacrylate
that have electron-withdrawing substituents on the double bond polymerize by an anionic, conjugate
addition pathway.
Copolymerization of two monomers gives a product with properties different from those of either
homopolymer. Graft copolymers and block copolymers are two examples.
Alkene polymerization can be carried out in a controlled manner using a Ziegler–Natta catalyst.
Ziegler–Natta polymerization minimizes the amount of chain branching in the polymer and leads to
stereoregular chains—either isotactic (substituents on the same side of the chain) or syndiotactic
(substituents on alternate sides of the chain), rather than atactic (substituents randomly disposed).
Step-growth polymers, the second major class of polymers, are prepared by reactions between
difunctional molecules, with the individual bonds in the polymer formed independently of one another.
Polycarbonates are formed from a diester and a diol, and polyurethanes are formed from a diisocyanate
and a diol.
The chemistry of synthetic polymers is similar to the chemistry of small molecules with the same
functional groups, but the physical properties of polymers are greatly affected by size. Polymers can be
classified by physical property into four groups: thermoplastics, fibers, elastomers, and thermosetting
resins. The properties of each group can be accounted for by the structure, the degree of crystallinity, and
the amount of cross-linking they contain.